Mordant triazole dyestuffs and process for making the same



. wherein R1 and Patented Nov. 21, 1944 236298 11 a. MORDANT TRIAZOLE DYESTUFFS AND I .i PROCESS FOR MAKING 'rnn SAME Achille Conzetti, Basel, and Otto 'Sclrmid, Muttcnz, near Basel, Switzerland, assignors to J. R. Geigy A. G., Basel, SwitzerlamL-a S wiss corporation No Drawing. Application October -20, 1941, Se-" rial No. 415,822. .In Switzerland November 26,

7 Claims. (Cl. 26 -308) r It'is known that o-aminoazo dyestuffs canbe converted into 2-aryl-1:3-arylentriazoles [by means of oxidation. As-suitable'oxidising agents there may .be cited salts of "the hypochlorites and cupric ,tetrammine' salts. Furthermore 'it is known that also o-nitro azodyestufis can becon-r verted into 2-aryl-1': 3-arylentriazoles; Alkali 'sul-' flutes and zinc-ammoniawater among oth'ershas become known as suitable reduction'agents'. Such 2-aryl-1:3-ary1entriazoles are colorless to globin and the like, into the corresponding triazoles.

, fSuitable diazo components for the manufacture of the azo dyestuffs coming into question are weakly yellowish bodies which are not dyestufis in the technical sense.- I V M ,7 I

It has now surprisingly been found that 2-aryl- 1:3 -arylentriazoles containing in both the arc matic nuclei'each timein orthoor'peri-position to a triazole nitrogen atom "still a metallisable group are converted in substance or on the fibre into colored complex compounds of a mostly for instance: 2-amino-l-hydroxybenzenee l-sulfonic acid andderivatives thereof substituted in 5-i'or 6-pos'ition- -by-halogen or nitro groups, 2,-amino-1-hydroxybenzene-6-sulfonic acid and its derivative substituted in ,4-position'by halogenor nitro groups, 2-amino-1-hydroxynaph- -thalene-l-sulfonic acid anditszderivatives subfstituted in the'non-aminated nucleuswith nitro yellow color by treatment-with metal yielding agents, such as chromium or copper yielding agents.v These complexv dyestufi metal I compounds are distinguished by a very good, in some cases by an excellent light,- fastness.

The new 2-.ary1-1:3 arylentriazoles according v to the present invention "correspond tolthe j formula' a l%-g\ RII I N,R2

- wherein R1 andRz each represents an aromatic radical, of the benzene or naphthalene series, at

least one being a naphthalene radical, X1 and X2 being members of the group consisting of OH, COQI- I, halogen and alkoxy each. situated in one of the'positionsorthojand perito the triazole ro p;

The above defined mordan t triazole compounds azo dyestuffs the general formula T Xi X2 are obtained for example by oxidation of o-amino R; mean aromatic radicals, whilst X1 and-X2 mean'metallisable groups, such as the hydroxyl or carboxyl group, standing in' orthoor in peri-position -to the azobridge or substituents which can be converted into metalv lisable groups such'as for instance, halogen oralkoxy groups." These compounds are converted,

by means of oxidation 'agentshsuch, as for example hydrogen peroxide per-borate; per-car- 4 bonate, per-sulfate, hypochlorite, permanganate,

compounds of the 'hexavalent chromium,- cupric tetramine sulfate and the like, in the absence or presence of oxidation catalysts such as copper powder, copper ions, iodine, iron sa1ts, haemo- 'For azocomponents the following compounds come i into consideration: 2-amin'onaphthal'ene- 3- carboxylic acid and derivativesthereof substituted in the non-carboxylated nucleus by nitro or sulfonic-acid groups and so on. Evenflb'y coupling diazotised Z-amino-l-hy- "droxybenzenes which are substituted in 4- or '5-positi'on by'fhalogen or nitr o groups or which possess in 4'-positi'on halogen'orf'an alkyl 'group ,and in 5 or 6-p0siti0n anitro group, with derivatives of the above enumerated coupling components containing 'sulfonic acid groups or with 1amino B-hydroxynaphthaliane-- or 5-sulfonic acid there are obtained suitable o-amino a zo dyestuffs.

V The oxidationof the o-amino azo dyestuffs to a so the'corresp onding triazole derivatives is preferably carried out in aqueous solution by'means of sodium hypochlorite. The reaction temperature varies accordin to the solubility or oxidisability j of the o-amino-azo dyestu'ff v and is advantageously chosen as low as possible." Thus, for example, there is worked at'2 0 C. or at a higher temperature. The use of oxidising catalysts, such as iodine or copper'powder are often of decisive importance for a smooth oxidation.

When compounds of the hexavalent chromium, such as bichromates or chromic acid, are used as oxidising agents, chromium compounds-of the triazoles are formed directly which without difiiculty,- after their conversion into the alkali salts, yield dyestufisof aivery' good levellingpower and often of very remarkable fastnes's to light.

If ammoniacal copper salt solutions are used 1 as oxidising agentsycopper complex compounds are immediately formed whichcan directly be used as highly lightfa'st pigments, which, however, can beconverted'into the metal free triazole derivatives'by removing the copper for instance by means ofsodium sulfide or'strong mineral acids.

' The metal free triazoles draw from an acid bath on ani mal fibre and give uniform chromium dyeings of high fastn ess to light by treatment with compounds of the 6-valent'jchromium. By

above defined mordant triazole compounds consists in that o-nitro azo dyestuffs of the general formula r r R;N=N-B1 N O z are converted in a manner known in itself by reduction (with alkali sulfides or zinc-ammonia water) into the corresponding 2-aryl-1r3-ary1entriazoles. In this formula R1, R2, X1 and X2 have the same meanings as in the former Formula I.

For the diazo components of the o-nitro azo dyestuifs the following o-nitro amino compounds come into consideration: 3-nitro-2-aminobenzoic acid, 3-nitro-2-amino-benzoic-5-sulfonic acid (obtained by sulfonating o-chlorobenzoic acid with oleum, nitrating the chlorosulfobenzoic acid with nitric acid-sulfuric acid mixture and heating the obtained 3-nitro+2-aminobenzoic -sulfonic acid with ammonia water in a closed vessel up to a higher temperature), 13.2.5-dinitro-2-aminobenzoic acid and so on. As coupling components there are suitable for instance: e-n-aphthol, 1- hydroxynaphthalene4- rand --5-;sulfonic acid, .2- hydroxynaphthalene l -5-, -6-, -'7 or B-sul- Ionic acid, amino or acylaminonaphthol sulfonic acids respectiveiy coupling in o-position to the hydroxyl group.

The reduction of the "o-nitro azo dyestuffs to the corresponding triazole compounds is carried out in known manner by treatment with alkali sulfidein an aqueous solution at a raised ternperature, e. g. at .80100 0., or 'with.zinc dust in ammonia water also at ara-ised temperature.

In some cases it is advantageous for the sulfide reduction to complete the vreaction by adding ,lit tle quantities of stronger reduction agents, such as sodium hydrosulflte or zinc and hydrochloric acid.

The products obtained according to both these 3 methods are mostly more .or less yellowcolored powders which draw, from an acid bath, colorless or with yellowish color .on animal fibres and give, by treatment with metal yielding agents, such as for example chromium salts, strong colorations of yellow to brownish yellow ,dyeings. The same are distinguished by good, in some cases even excellent fastness to light.

The present invention is illustrated by the following examples, wherein the parts are'by weight, unless otherwise stated.

EXAMPLE 1 thalene-3-car'boxyiicacid (disodium saltt aredissolved in sec parts of hot water, the red solution cooled to 45 (1. and whilst stirring 70 parts of sodium hypoohlorite solution, produced by saturating a 17% caustic soda lye with chlorine, are dropped in within 60 minutes. By the addition of 50 parts of sodium chloride, the :new dyestuff partly separated from the yellow solution, is precipitated completely; it is filtered oil by suction and dried. The greenish yellow powder is .soluble in water with a yellow color and with a weak greenish-yellow color "in concentrated sulfuric acid.

The new dyestui f dyes wool from the acid bath in greenish-yellow shades which become more intensive by after-chroming. The general fastnesses are good, the light fastness is very excellent. The new dyestuff corresponds to the for- ,mula

' coon on Hmong-O l0 I d U .By nitrating ,in concentrated sulfuric acid a .15 nitro derivative is obtained, an orange powder,

which dyes wool acid in light yellow, afterchromed in yellow shades.

Instead of the amino azo dyestuff with 4- :chloro 2 amino 1 hydroxybenzene 6 -.su1

20 ionic acid used in the above example there may be used quite well an amino azodyestuff with 2- amino 4 1-- hydroxybenzene- 4 sulfonic acid, 5-

chloro 2 amino -1 hydroxybenzene 4 sul-= ionic acid or 6-chloro-2-amino.1-hydroxybenzene--sulfonic acid. The dyestuffs thus obtained are similar to the dyestufis described.

EXAMPLE 2 466 parts of the o-aminc-azo dyestuff, used in Example 1., are dissolved in 1000 parts of hot water and whilst stirring a copper tetramine sulfate solution of 50 parts of crystallised copper sulfate, .200 parts of water and 56 parts of 25% ammonia water are allowed to flow in within 5 minutes. Whilst passing air through, stirring .is carried out at 90-100 C. until the precipitate first colored brown, then ,olive green, has become pure greenish yellow, which occurs after about 20 hours. The completely formed copper compound is then sucked off, washed and dried. It is a highly 'lightfast pigment insoluble in water, alcohols and fats. The formation of the new compound is effected substantially quicker when the oxidation is completed with a little hydrogen per- 5 oxide or sodium hypochlorite.

The same insoluble copper compound is also obtained with other copper-yielding agents, for

example copper acetate.

The copper-flee dyestuff is obtained therefrom by the following process:

53 partsof the-copper compound are suspended in 300 parts of boiling water .and a solution of 24 parts of crystallised sodium sulfide in 100 parts of water is added, whilst the yellow sodium salt 55 of the dyestuff, with separation of copper sulfide, passes into solution. Stirring is carried out for 10 minutes at 90 0., then it is filtered, the dyestufi separated with 50 parts of sodium chloride, allowed to cool, drawn :off and dried.

45 parts or a yellow powder are obtained, which is identical with the dyestuff in Example 1.

EXAMPLE 3 13 parts of the o-amino azo dyestuff, used in 5 Example 1, are dissolved in 650 parts of hot water and whilst stirring, a solution of 4 parts of crystallised sodium bichromate and 3.5 parts of concentrated hydrochloric acid in 50 parts of water is dropped in at 95-100 C. within 30 minutes. The red solution is first colored brown-red, then greenish and finally green yellow. After 4 hours neutralisation. is effected with 1 part of anhydrous sodium carbonate and clarified. On the addition of 60 parts of sodium chloride the chromium compound is precipitated from the yel- "-80-90 Q. into the red orange solution. Under separationof sulfur the solution becomes orange low solution as a brownish yellow powder. -.It"

is filtered off ,by suction and dried. The chrofor example 2% formic acid bath in very uniform, highly, lightfast greenish-yellow shades.

. The same chromium compound is also obtained usual methods, for example by boiling the wi e-1 I mium compound dyes wool from a weak acid,

by treating the dyestufi, obtained according to;-;,-

Example 1, with chromium yieldingagents by yellow colored. It is clarified and treated at 50- 60 C. with the necessary quantity of sodium hydrosulfite required for obtaining a pure yellow final color of the solution (consumption 10-12 parts of hydrosulfite). Then the whole is still maintained for -30minutes-at, 60 (3., acidified with 35 parts offconcentratedhydrochloric acid ous solution with chromium acetate and subsel andheated up. Already in the heat the triazole quentconversion with sodium carbonate. dyestufl begins to precipitate out in form of light g EXAMPLE 4 yellow crystals. Finally the whole is treated with m r t 50.parts of hydrochloric-acid, allowed to cool 'f-f101.5 partsof the acid coupled dyestufi from down, sucked off and dried, iezo 4 C 1 2 amino yd ih .5 The dyestufl dyes wool ,froman acid bath with b n enerfi-sulfonic acid and l-'amino-8hyd uxyl yellowish shades which lay-treatment with salts 1 94 6 -8 0 1 acid a dissolved as (1 of the hexavalent chromium change into strong mm um salt in 1000 pa o hot Water and reddish yellow dyeings of good fastness. The new dropped at 80 Cfwithin 30 min'utes into a cupric dyestuff corresponds to. the formula te'tr'amine sulfate solution prepared from 100 20 parts ;of crystallised copper sulfate, 500 partsof not water and 112 parts of 2.5% ammonia. Stir- K Q ring is efiected for 2 hours at 90 C. whilst intro- 1 ducing air, whereby the copper compound of the I new dyestuflf separates out'for the most part as 1108s an olive-yellow powder. Aftencooling it is sucked ofi', suspended in 1000 parts of hot water, a solu- EXAMPLE; 6, tion of 96 parts of crystallised sodium sulfide in r 500' parts of water is allowed to'drop in within "40 parts of the dyestufi' obtained from diazo- 15 minutes, stirring is effected for about another 0 tised 2i5 dichlo'roaniline-3-sulfonic acid (or 2- 15 minutes at-90 C. and then it is filtered from br'omo-5 chloroaniline-S-Sulfonic acid) and 2- the copper sulfide. From the yellow-brown soluaminO'naphthaIene -B-carboxylic acid are dis tion of v the sodium salt of the new dyestufi an solved in 1000 parts of water and the red solution olive-brown powder is precipitated with acetic is dropped. while well stirring: at 90-100 C; acid-and sodium chloride. The-new dyestulf diswithin 15 minutes into a' copper tetramine sulsolves in water witha yellow-brown color and fate solution, which has beenprepared by dis; dyes wool, after-chromed, lightfast brown-yellow. solving 25 parts of crystallised copper sulfate. in The new. dyestufi' corresponds'to the formula 200 'parts of water and treating with 40 parts of 1 0H ammonia water (25% NH3) Stirring is efiected s 03H 49 for 8 hours at 90-100 C., while air is introduced, and the insoluble brown yellow precipitate is filtered off by suction.-

v 3, The said precipitate issuspended in 400 parts I of water and boiled for 30 minutes with the solu- Hdtion of 24 parts of crystallised sodium sulfide in v p 100 parts of water. It is filtered from black cop- Instead of the dyestufi used in the above exam- De Sulfide, Which has Separated Out, d the ple a similar dyestuff with 6-nitro-2 a'min0- 1- stuff is precipitatedein form of a y llow Powder hydroxynaphthalene-4-su1f0nic acidmay be used from the yellow filtrate, by adding, while stirring, as diazo component, whilst for the'coupling-com- 5D parts Of Sodiumv Chloridev dyestufi y ponent there'may be used 2-.amin'onaphthalene- W0 e lowi h fr m n a bath; y tmen 3 -c'arboxylic acid. h with salts of the hexavalent chromium yellow I ,EXAMPLE 1 dyeings of excellent fastness to light are obtained. r v v v A dyestuff of similar properties is obtained by I 46.1 parts of the o-nitro dyestufl, 3-nitro-2- coupling in the-above example, instead of diazoamino-5-sulfobenzoic acid fl-naphthol, are distised 2;5-dichIorOaniIine-B-sulfonic acid, 2-ethsolved in 450 parts of hot water and, whilst stiroxy-5-chloroaniline-3-sulfonic acid with 2-ami-- 'ring, 30 parts of an ammonium sulfide solution nonaphthalene-3-carboxylic acid and working up,

(corresponding to 6.8 parts (NH4)2S) dropped at in the same manner as above described. Table I I Shade of wool dyeing No. o-Aminoazo dyestiifi g C2312; I i i powder 0 Acid Chromed 1 6-nitro 2-amino-l-hydroxybenzene-Lsulfonic acid NaClO Y ellowi s. Yellow... 'Greenish light yellow. j '"'12-ammonaphthalene-3-carboigylic acid. 7 I

2 4-nitro 2-amino-l-hydroxybenzcne-fi-sulfonic acid do do Light yellow Light yellow.

2-am1n0naphthalene-S-carboxylic acid. 3 5-nitro-2-amino-l-hydroxybenzene 2-amino-3-cardo Yellow.

boxynaphthalene-S-sulfonic acid. 4 4-chloro-5-nitro-2-amino-l-hydroxybeuzene 2-aminodo D0.

3-carboxynaphthalene-B-sulfonic acid. "I 5 4-methyl-5-nitro-2-amino-1-hydroxybenzene 2- do Reddish-yellow.

amino-3-carboxynaphthalene-G-sulfonic acid. 6 4-chloro-2-amlno-1-hydroxybenzene 1:8-amino-naph- Copper amine Brown Browhish-yellow.. Brown-yellow.

, thol-4-sull'onic acid, acid coupled. solution Table I I l I l Treated C 010: Shade of wool dyeing No o-Nitro azo dyestuii with of the Pwder Acid Chromed 7 3-nitro-2-amino benzcic acid l-hydroxynaphthalene--sulfonic acid- (NHD S Yel1ow.. Yel1owish Reddish-yellow. '8 3-nitro-2-amino-benzoic acid l-hydroxynaphthalene-5-siflionic acid. do ..do. o Do.

9 B-nitro-Z-amino-benzoic acid Z-hydroxynaphthalene-i-sulfonic acid- .do do. .do c Do.

10' 3-nitr'o-2amino-benzcic acid 2-hydroxynaphthalene-S-sulionic acid- .do do .do Do.

3ES-dinitro-Z-aminobenzoio acid yields similar I dyestufis with the coupling components cited in the dyestuffs 7-10, also when in the above dyestuffs the 2-hydroxynaphthalene-4- and -6-sulfonic acid is replaced by the corresponding -5-, -'7- and -8-sulfonic acid.

What we claim is: 1. Process for the manufacture of mordant dyestuffs of the 2-aryl-1z3-arylentriazole series which comprises treating with an oxidizing agent an o-aminoazodyestufi containing sulfonic acid groups of the general formula wherein R1 and R2 mean aromatic radicals of the benzene and naphthalene series, at least one being a naphthalene radica1,,X1 and X2 being members of the group consisting of OH, COOH, halogen and alkoxy groups each situated in one of the positions @ortho and peri to the azo group, and :at least one of X1 and 'X2 being an OH group in ortho-position. to the azo group.

. 2., Process for the manufacture of mordant dyestuffs of the 2-aryl-1:3-arylentriazole series which comprises treating with an oxidizing agent an -oaminoazo dyestufi' containing sulfonic acid groups of the formula Hoes- Cl R2 being a naphthalene radical substituted in o-position'to the azo group by an amino group and bearing the substituent X2, selected from the group consisting of OH, COOH, halogen and OH m1 coon HOaS N= N .4. The metallizable 2-aryl-1:3-arylentriazole dyestuffs containing sulfonic acid groups and corresponding to the formula l I R /N-R;

wherein Riand R2 mean aromatic radicals of the benzene and naphthalene series, at least one being a naphthalene radical, X1 and X2 being members of the group consisting of OH, COOH, halogen and alkoxy groups each situated in one of the positions ortho and pe'ri to the triazole group, and at least one of X1 and X2 being an OH group in ortho-position to the triazole group dyeing wool after-chromed in yellow light fast shades. a

5. The metallizable 2-aryl-1:B-arylentriazole dyestufi of the formula 011 HOaS N\ being a greenish yellow powder, dissolving in water with yellow color and in concentrated sulfuric acid with a weak greenish-yellow color, dyeing wool from an acid bath in greenish-yellow shades which become more intensive by after-chroming.

6. The metallizable Z-aryl-l:3-arylentriazol'e dyestuff of the formula being a yellow-brown powder dyeing wool from an acid bath in brownish-yellow shades which increase powerfully .in strength by after-chroming.

7. The metallizable 2-aryl-1:3-arylentriazole dyestuff of the .formula OOOH being a yellow powder dyeing wool from an acid bath in yellow shades which turn by afterchroming into reddish-yellow shades of excellent fastness properties.

ACHILLE CONZETTI. OTTO SCHM'ID. 

